CN112812347A - Optical thin film material, preparation method thereof and polarizer - Google Patents
Optical thin film material, preparation method thereof and polarizer Download PDFInfo
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- CN112812347A CN112812347A CN202110203205.XA CN202110203205A CN112812347A CN 112812347 A CN112812347 A CN 112812347A CN 202110203205 A CN202110203205 A CN 202110203205A CN 112812347 A CN112812347 A CN 112812347A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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Abstract
The invention is suitable for the technical field of materials, and provides an optical film material, a preparation method thereof and a polarizer, wherein the preparation method of the optical film material takes polymethyl methacrylate (PMMA) as a base material, and can well improve the high-temperature resistance and the toughness of the film material by introducing Polycarbonate (PC) with high-temperature resistance and high toughness; and the chalcone functional group polymethyl methacrylate resin (birefringence regulator) which can be well dispersed in a material system and is well compatible with materials in the system is introduced, and a double-screw extruder and a single-screw extruder are adopted to be matched with extrusion film forming equipment for use, so that the good compatibility of PC and PMMA can be ensured, the optical film material prepared by blending not only has good high-temperature resistance, but also has a phase difference regulation function, the problem of single negative birefringence of the traditional PMMA is well solved, and the diversified requirements of the current market on the optical film can be met.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an optical thin film material, a preparation method thereof and a polarizer.
Background
Polarizers are important materials of components indispensable for flat panel displays. In recent years, as the price of flat panel display products has dropped, more manufacturers have been forced to seek more ways to reduce the production cost of the products in order to secure their sales profits, etc., and it has become a major trend to reduce the number of materials used by compounding a polyvinyl alcohol (PVA) support substrate of a polarizer, a retardation plate, and other functional optical films. Therefore, the development and research of the optical film with the phase difference compensation function have good market prospect.
Polymethyl methacrylate (PMMA) has very high light transmittance, high mechanical strength and good chemical stability, and is the most ideal optical film material for the polarizer. However, the glass transition temperature of PMMA resin is less than 110 ℃, the high temperature resistance is poor, the water absorption rate is as high as 0.3% -0.4%, and the side chain of the molecular chain contains polar group, which has negative birefringence, which will definitely seriously limit the application range of the PMMA resin in the optical film of the polarizer. However, a methacrylic resin having a novel structure designed in the prior art, in which a graft polymerization copolymer obtained by graft polymerization of a vinyl polymerizable monomer is contained in a polymer to form a core-shell structure, has high heat resistance, excellent mechanical properties and high light transmittance, but has not yet solved the problem of negative birefringence of an optical film produced therefrom, and has not yet been widely applicable to diverse needs in the polarizer field.
Therefore, the existing PMMA has the characteristics of poor high temperature resistance and single negative birefringence, namely, the PMMA does not have the adjusting function of phase difference compensation, and cannot meet the diversified requirements of the current market on optical films.
Disclosure of Invention
The embodiment of the invention provides a preparation method of an optical film material, and aims to solve the problems that the existing PMMA is poor in high-temperature resistance and has the characteristic of single negative birefringence, namely, the PMMA does not have a phase difference compensation adjusting function and cannot meet the diversified requirements of the existing market on the optical film.
The embodiment of the invention is realized in such a way that the preparation method of the optical film material comprises the following steps:
weighing the following components in parts by weight: 50-70 parts of polymethyl methacrylate, 15-35 parts of polycarbonate, 5-15 parts of birefringence regulator, 0.05-1 part of antioxidant and 0.5-2 parts of dispersant; wherein the birefringence regulator is chalcone functional group polymethyl methacrylate resin;
blending the polymethyl methacrylate, the polycarbonate, the birefringence regulator, the antioxidant and the dispersing agent, and then conveying the blended materials to a double-screw extruder for melt blending extrusion to obtain a blended material, wherein the temperature of the double-screw extruder is 225-290 ℃, and the rotating speed of the double-screw extruder is 15-100 r/min;
drying the blend, conveying the blend to a single-screw extruder, and extruding the blend to form a film to obtain an optical film material, wherein the temperature of the single-screw extruder is 225-285 ℃, and the extrusion speed is 10-100 r/min; the temperature of the winding cold roll is 30-80 ℃.
The embodiment of the invention also provides an optical film material, which is prepared by the preparation method of the optical film material.
The embodiment of the invention also provides a polarizer, which is prepared by compounding the optical film material, the polyvinyl alcohol material and other functional films.
According to the preparation method of the optical film material provided by the embodiment of the invention, polymethyl methacrylate (PMMA) is taken as a base material, Polycarbonate (PC) with high temperature resistance and high toughness and chalcone functional group polymethyl methacrylate resin (birefringence index regulator) which can be well dispersed in a material system and is well compatible with materials in the system are introduced, and a double-screw extruder and a single-screw extruder are adopted to extrude a film forming device for matching use, so that the good compatibility of the PC and the PMMA can be ensured, the optical film material prepared after blending not only has good high temperature resistance, but also has a phase difference regulation function, the problem of single negative birefringence of the traditional PMMA is well solved, and the diversified requirements of the market on the optical film can be met. Meanwhile, the preparation method can realize continuous production, greatly improves the working efficiency, does not use a large amount of organic solvent in the whole preparation process, is green and environment-friendly, has wide market prospect, and is suitable for popularization and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
According to the preparation method of the optical film material provided by the embodiment of the invention, polymethyl methacrylate (PMMA) is taken as a base material, and the toughness and the high-temperature resistance of the film material can be well improved by introducing Polycarbonate (PC) with high-temperature resistance and high toughness; and the chalcone functional group polymethyl methacrylate resin (birefringence regulator) which can be well dispersed in a material system and is well compatible with materials in the system is introduced, and a double-screw extruder and a single-screw extruder are adopted to be matched with film extruding equipment for use, so that the good compatibility of PC and PMMA can be ensured, the optical film material prepared after blending not only has good high-temperature resistance, but also has a phase difference regulating function, and the problem of single negative birefringence of the traditional PMMA is well solved.
The embodiment of the invention provides a preparation method of an optical thin film material, which comprises the following steps:
step 101, weighing the following components in parts by weight: 50-70 parts of polymethyl methacrylate, 15-35 parts of polycarbonate, 5-15 parts of birefringence regulator, 0.05-1 part of antioxidant and 0.5-2 parts of dispersant; wherein the birefringence regulator is a chalcone functional group polymethyl methacrylate resin.
Wherein, the chalcone functional group polymethyl methacrylate resin can be any one of methyl methacrylate-co-chalcone methacrylate copolymer, methyl methacrylate-co-aminochalcone methacrylate copolymer or methyl methacrylate-co-methoxy chalcone methacrylate copolymer.
102, blending the polymethyl methacrylate, the polycarbonate, the birefringence index regulator, the antioxidant and the dispersing agent, and then conveying the blended materials to a double-screw extruder for melt blending extrusion to obtain a blended material, wherein the temperature of the double-screw extruder is 225-290 ℃, and the rotating speed is 15-100 r/min.
In a preferred embodiment of the present invention, the rotation speed of the twin-screw extruder is set to 30 to 80r/min, and the temperature of the melting section thereof is set to 230 to 270 ℃.
103, drying the blend, and conveying the blend to a single-screw extruder to extrude the blend into a film to obtain an optical film material, wherein the temperature of the single-screw extruder is 225-; the temperature of the winding cold roll is 30-80 ℃.
In the preferred embodiment of the invention, the rotating speed of the single-screw extruder is set to be 30-60r/min, and the extrusion temperature is set to be 235-270 ℃.
The invention adopts the plastic physical modification concept, takes polymethyl methacrylate as a base material, introduces the copolymerized PC material with high temperature resistance and high toughness and synthesizes the birefringence index regulator with good compatibility with the copolymerized PC material, ensures the compatibility of PC and PMMA and ensures that the optical film prepared by blending has the phase difference regulation function.
In the embodiment of the present invention, polymethyl methacrylate is a main raw material of the optical film material, which is a resin material having good transparency. Preferably, the polymethyl methacrylate is a copolymer type polymethyl methacrylate, and the average molecular weight thereof is 7 to 13 ten thousand. The copolymer-type polymethyl methacrylate includes, but is not limited to, an alicyclic structure, a heterocyclic structure, or a structure containing an aromatic group in the constituent unit. For example, a copolymer PMMA brand of R100 of Japan Electrochemistry may be used.
In the embodiment of the invention, polycarbonate is introduced into the material system, the partial negative PMMA can be compensated by utilizing the positive birefringence characteristic of the polycarbonate, and the high glass transition temperature can enhance the high temperature resistance of the PMMA. In the present invention, it is preferable to use a copolymerized polycarbonate having low water absorption, excellent heat resistance, low temperature characteristics and surface hardness, a glass transition temperature of not less than 160 ℃ and an average molecular weight of 4.5 to 9.0 ten thousand. For example, APEC 2097, available under the trade mark bayer, germany, may be used.
Before all the materials are mixed and blended, polymethyl methacrylate and polycarbonate are blended and extruded to prepare a master batch, the master batch is frozen and crushed in liquid nitrogen to obtain master batch powder with the average particle size of not more than 50 mu m, and the master batch powder, a birefringence regulator, an antioxidant and a dispersing agent are blended and then conveyed to a double-screw extruder for melt blending and extrusion.
According to the theory that different chain segments in the copolymer molecule mutually repel to cause compatibility, the copolymerization PMMA and the copolymerization PC are respectively adopted, and the particle size of the crushed material is controlled by means of liquid nitrogen freezing and crushing, so that the blending effect of each phase can be improved, the compatibility of PMMA and PC phases is promoted to be improved, and the transparency of the optical film is enhanced.
In a preferred embodiment of the present invention, the birefringence modifier is a methyl methacrylate-co-chalcone methacrylate copolymer, and the preparation method thereof is as follows:
under the protection of nitrogen, adding a mixture of methyl methacrylate and chalcone methacrylate into an emulsifier aqueous solution with the mass fraction of 0.1-0.5%, stirring and mixing uniformly, heating to 50-80 ℃, adding an initiator, and continuing to react until the reaction is finished to obtain methyl methacrylate-co-chalcone methacrylate copolymer emulsion; and (3) freeze-drying the methyl methacrylate-co-chalcone methacrylate copolymer emulsion to obtain the methyl methacrylate-co-chalcone methacrylate copolymer.
In the embodiment of the invention, the temperature of the uniformly stirred and mixed substance is raised to 50-80 ℃, and a water bath heating mode can be adopted. Of course, other temperature raising methods may be adopted, and the present invention is not limited thereto.
In the embodiment of the invention, the copolymerization type PC is introduced, and the content of chalcone Methacrylate (MSPK) in the birefringence regulator is adjusted to counteract with the negative birefringence PMMA to a certain extent; on the premise of determining the proportion of PMMA/PC blend to meet the mechanical property, the random conversion of positive and negative birefringence of different films can be realized by adjusting the proportion of Methyl Methacrylate (MMA) and MSPK, and the operation is simple. Specifically, the mixing mass ratio of methyl methacrylate to chalcone methacrylate in the mixture of methyl methacrylate and chalcone methacrylate is 1-4: 1-4.
In the embodiment of the invention, the birefringence regulator is synthesized by adopting an emulsion polymerization method, the viscosity of an emulsion polymerization system is still very low after the reaction reaches a high conversion rate, a dispersion system is stable, the proportion of MMA and MSPK is easy to control, and the realization of the functional design of the birefringence regulator is facilitated; meanwhile, the prepared birefringence regulator PMMA-CO-PMSPK has a group for copolymerizing PMMA on one hand, and ketone ester of PMSPK is similar to an internal functional group of copolymerizing PC on the other hand, so that a good compatibilization effect can be achieved.
In the embodiment of the invention, the particle size of the methyl methacrylate-co-chalcone methacrylate copolymer can be adjusted by the type and content of the initiator. Preferably, the molecular weight of the methyl methacrylate-co-chalcone methacrylate copolymer is controlled between 6 ten thousand and 12 ten thousand, and the average particle size of the copolymer is not more than 50 mu m.
In the embodiment of the present invention, the antioxidant is a hindered antioxidant or a phosphite antioxidant. Preferably, the antioxidant is used by matching antioxidant 1010 and antioxidant 168, wherein the ratio of the antioxidant 1010 to the antioxidant 168 is 2: 1.
The dispersant is at least one of siloxane dispersant, stearate dispersant or wax dispersant.
The embodiment of the invention also provides an optical film material, which is prepared by the preparation method of the optical film material. The optical film material is prepared by the preparation method, so that the optical film material has good high-temperature resistance and phase difference compensation function, and can meet the diversified requirements of the current market on the optical film.
The embodiment of the invention also provides a polarizer, which is prepared by compounding the optical film material, the polyvinyl alcohol (PVA) material and other functional films. The optical film material has good high temperature resistance and phase difference compensation function, and can be suitable for preparing the polaroid required by a flat panel display.
Examples of certain embodiments of the invention are given below, which are not intended to limit the scope of the invention. Unless otherwise indicated, the starting materials used in the examples of the present invention are either commercially available or prepared by conventional methods. For example, polymethyl methacrylate (PMMA) is HR-1000L, available from Coly, Japan. Polycarbonate (PC) was APEC 2097, manufactured by Costa, and its glass transition temperature was 210 ℃.
Example 1
The preparation steps of the optical film material of the embodiment of the invention are as follows:
weighing the following components in parts by weight for later use: 55 parts of polymethyl methacrylate, 35 parts of polycarbonate, 10 parts of birefringence regulator, 0.1 part of antioxidant (antioxidant 1010) and 0.5 part of dispersant (stearate).
Wherein, the birefringence regulator (methyl methacrylate-co-chalcone methacrylate copolymer) is synthesized by adopting an emulsion polymerization method, and the specific preparation method comprises the following steps: uniformly dissolving an emulsifier (sodium dodecyl benzene sulfonate) in deionized water to prepare an emulsifier aqueous solution with the mass fraction of 0.1%, then pouring the emulsifier aqueous solution into a four-mouth bottle, introducing nitrogen for protection, setting the rotating speed of a magnetic stirrer to be 600rpm, uniformly mixing 60 parts of MMA and 40 parts of MSPK by using an ultrasonic cleaner to obtain a mixture of methyl methacrylate and chalcone methacrylate, adding the mixture into a reaction system of the four-mouth bottle, uniformly stirring and mixing, and heating in a water bath, wherein the water bath temperature is controlled at 60 ℃. After the reaction system is heated to the set temperature of 60 ℃, adding an initiator (sodium persulfate) accounting for 1% of the mass of the reaction system to react until the reaction is finished, and obtaining methyl methacrylate-co-chalcone methacrylate copolymer emulsion; and (3) freeze-drying the methyl methacrylate-co-chalcone methacrylate copolymer emulsion to obtain the methyl methacrylate-co-chalcone methacrylate copolymer.
Blending and extruding polymethyl methacrylate and polycarbonate to prepare a master batch, freezing and crushing the master batch in liquid nitrogen to obtain master batch powder with the average particle size of not more than 50 mu m, blending the master batch powder with a birefringence index regulator, an antioxidant and a dispersing agent, and feeding the mixture into a double-screw extruder through a feeding hopper to perform melt blending and extrusion to obtain a blend; wherein the temperature of the double-screw extruder is 250 ℃, and the extrusion rotating speed is 60 r/min; drying in a forced air oven at 110 deg.C; extruding the prepared blend on a single-screw extruder to form a film, wherein the temperature of the single-screw extruder is 265 ℃, and the extrusion speed is 60 r/min; and (3) rolling the cold roll at the temperature of 70 ℃, and discharging the sheet on the cold roll to obtain the optical film material.
Example 2
The preparation steps of the optical film material of the embodiment of the invention are as follows:
weighing the following components in parts by weight for later use: 50 parts of polymethyl methacrylate, 35 parts of polycarbonate, 15 parts of birefringence regulator, 0.1 part of antioxidant (antioxidant 1010) and 0.5 part of dispersant (stearate).
Among them, the preparation method of the birefringence modifier (methyl methacrylate-co-chalcone methacrylate copolymer) was the same as that of example 1.
Blending and extruding polymethyl methacrylate and polycarbonate to prepare a master batch, freezing and crushing the master batch in liquid nitrogen to obtain master batch powder with the average particle size of not more than 50 mu m, blending the master batch powder with a birefringence index regulator, an antioxidant and a dispersing agent, and feeding the mixture into a double-screw extruder through a feeding hopper to perform melt blending and extrusion to obtain a blend; wherein the temperature of the double-screw extruder is 250 ℃, and the extrusion rotating speed is 60 r/min; drying in a forced air oven at 110 deg.C; extruding the prepared blend on a single-screw extruder to form a film, wherein the temperature of the single-screw extruder is 265 ℃, and the extrusion speed is 60 r/min; and (3) rolling the cold roll at the temperature of 70 ℃, and discharging the sheet on the cold roll to obtain the optical film material.
Example 3
The preparation steps of the optical film material of the embodiment of the invention are as follows:
weighing the following components in parts by weight for later use: 60 parts of polymethyl methacrylate, 32 parts of polycarbonate, 8 parts of birefringence regulator, 0.05 part of antioxidant (antioxidant 1010) and 0.8 part of dispersant (stearate).
The birefringence index regulator (methyl methacrylate-co-chalcone methacrylate copolymer) is synthesized by adopting an emulsion polymerization method, and the specific preparation method comprises the following steps: uniformly dissolving an emulsifier in deionized water to prepare an emulsifier aqueous solution with the mass fraction of 0.3%, then pouring the emulsifier aqueous solution into a four-mouth bottle, introducing nitrogen for protection, setting the rotation speed of a magnetic stirrer to 600rpm, uniformly mixing 40 parts of MMA and 60 parts of MSPK by using an ultrasonic cleaner to obtain a mixture of methyl methacrylate and chalcone methacrylate, adding the mixture into a reaction system of the four-mouth bottle, uniformly stirring and mixing, and heating in a water bath, wherein the water bath temperature is controlled at 80 ℃. After the reaction system is heated to the set temperature of 80 ℃, adding an initiator (sodium persulfate) accounting for 2 percent of the mass of the reaction system for reaction until the reaction is finished to obtain methyl methacrylate-co-chalcone methacrylate copolymer emulsion; and (3) freeze-drying the methyl methacrylate-co-chalcone methacrylate copolymer emulsion to obtain the methyl methacrylate-co-chalcone methacrylate copolymer.
Blending and extruding polymethyl methacrylate and polycarbonate to prepare a master batch, freezing and crushing the master batch in liquid nitrogen to obtain master batch powder with the average particle size of not more than 50 mu m, blending the master batch powder with a birefringence index regulator, an antioxidant and a dispersing agent, and feeding the mixture into a double-screw extruder through a feeding hopper to perform melt blending and extrusion to obtain a blend; wherein the temperature of the double-screw extruder is 230 ℃, and the extrusion rotating speed is 100 r/min; drying in a forced air oven at 110 deg.C; extruding the prepared blend on a single-screw extruder to form a film, wherein the temperature of the single-screw extruder is 285 ℃, and the extrusion speed is 10 r/min; and (3) rolling the cold roll at the temperature of 30 ℃, and discharging the sheet on the cold roll to obtain the optical film material.
Example 4
The preparation steps of the optical film material of the embodiment of the invention are as follows:
weighing the following components in parts by weight for later use: 70 parts of polymethyl methacrylate, 15 parts of polycarbonate, 15 parts of birefringence regulator, 0.5 part of antioxidant (a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 2: 1), and 0.8 part of dispersant (siloxane).
The birefringence index regulator (methyl methacrylate-co-chalcone methacrylate copolymer) is synthesized by adopting an emulsion polymerization method, and the specific preparation method comprises the following steps: uniformly dissolving an emulsifier in deionized water to prepare an emulsifier aqueous solution with the mass fraction of 0.5%, then pouring the emulsifier aqueous solution into a four-mouth bottle, introducing nitrogen for protection, setting the rotation speed of a magnetic stirrer to 600rpm, uniformly mixing 60 parts of MMA and 40 parts of MSPK by using an ultrasonic cleaner to obtain a mixture of methyl methacrylate and chalcone methacrylate, adding the mixture into a reaction system of the four-mouth bottle, uniformly stirring and mixing, and heating in a water bath, wherein the water bath temperature is controlled at 70 ℃. After the reaction system is heated to the set temperature of 70 ℃, adding an initiator to react until the reaction is finished, and obtaining methyl methacrylate-co-chalcone methacrylate copolymer emulsion; and (3) freeze-drying the methyl methacrylate-co-chalcone methacrylate copolymer emulsion to obtain the methyl methacrylate-co-chalcone methacrylate copolymer.
Blending and extruding polymethyl methacrylate and polycarbonate to prepare a master batch, freezing and crushing the master batch in liquid nitrogen to obtain master batch powder with the average particle size of not more than 50 mu m, blending the master batch powder with a birefringence index regulator, an antioxidant and a dispersing agent, and feeding the mixture into a double-screw extruder through a feeding hopper to perform melt blending and extrusion to obtain a blend; wherein the temperature of the double-screw extruder is 290 ℃, and the extrusion rotating speed is 80 r/min; drying in a forced air oven at 110 deg.C; extruding the prepared blend on a single-screw extruder to form a film, wherein the temperature of the single-screw extruder is 265 ℃, and the extrusion speed is 50 r/min; and (3) rolling the cold roll at 50 ℃, and discharging the sheet on the cold roll to obtain the optical film material.
Example 5
The preparation steps of the optical film material of the embodiment of the invention are as follows:
weighing the following components in parts by weight for later use: 65 parts of polymethyl methacrylate, 30 parts of polycarbonate, 5 parts of a birefringence regulator, 1 part of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1), and 2 parts of a dispersant (polyethylene wax).
The birefringence index regulator (methyl methacrylate-co-chalcone methacrylate copolymer) is synthesized by adopting an emulsion polymerization method, and the specific preparation method comprises the following steps: uniformly dissolving an emulsifier in deionized water to prepare an emulsifier aqueous solution with the mass fraction of 0.4%, then pouring the emulsifier aqueous solution into a four-mouth bottle, introducing nitrogen for protection, setting the rotation speed of a magnetic stirrer to 600rpm, uniformly mixing 60 parts of MMA and 40 parts of MSPK by using an ultrasonic cleaner to obtain a mixture of methyl methacrylate and chalcone methacrylate, adding the mixture into a reaction system of the four-mouth bottle, uniformly stirring and mixing, and heating in a water bath, wherein the water bath temperature is controlled at 50 ℃. After the reaction system is heated to the set temperature of 50 ℃, adding an initiator (sodium persulfate) accounting for 2% of the mass of the reaction system to react until the reaction is finished, and obtaining methyl methacrylate-co-chalcone methacrylate copolymer emulsion; and (3) freeze-drying the methyl methacrylate-co-chalcone methacrylate copolymer emulsion to obtain the methyl methacrylate-co-chalcone methacrylate copolymer.
Blending and extruding polymethyl methacrylate and polycarbonate to prepare a master batch, freezing and crushing the master batch in liquid nitrogen to obtain master batch powder with the average particle size of not more than 50 mu m, blending the master batch powder with a birefringence index regulator, an antioxidant and a dispersing agent, and feeding the mixture into a double-screw extruder through a feeding hopper to perform melt blending and extrusion to obtain a blend; wherein the temperature of the double-screw extruder is 270 ℃, and the extrusion rotating speed is 30 r/min; drying in a forced air oven at 110 deg.C; extruding the prepared blend on a single-screw extruder to form a film, wherein the temperature of the single-screw extruder is 270 ℃, and the extrusion speed is 50 r/min; and (3) rolling the cold roll at the temperature of 80 ℃, and discharging the sheet on the cold roll to obtain the optical film material.
Example 6
The preparation steps of the optical film material of the embodiment of the invention are as follows:
weighing the following components in parts by weight for later use: 67 parts of polymethyl methacrylate, 20 parts of polycarbonate, 13 parts of a birefringence regulator, 0.2 part of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1), and 0.7 part of a dispersant (siloxane).
The birefringence index regulator (methyl methacrylate-co-chalcone methacrylate copolymer) is synthesized by adopting an emulsion polymerization method, and the specific preparation method comprises the following steps: uniformly dissolving an emulsifier in deionized water to prepare an emulsifier aqueous solution with the mass fraction of 0.2%, then pouring the emulsifier aqueous solution into a four-mouth bottle, introducing nitrogen for protection, setting the rotation speed of a magnetic stirrer to 600rpm, uniformly mixing 60 parts of MMA and 40 parts of MSPK by using an ultrasonic cleaner to obtain a mixture of methyl methacrylate and chalcone methacrylate, adding the mixture into a reaction system of the four-mouth bottle, uniformly stirring and mixing, and heating in a water bath, wherein the water bath temperature is controlled at 50 ℃. After the reaction system is heated to the set temperature of 50 ℃, adding an initiator (sodium persulfate) accounting for 1.5 percent of the mass of the reaction system for reaction until the reaction is finished to obtain methyl methacrylate-co-chalcone methacrylate copolymer emulsion; and (3) freeze-drying the methyl methacrylate-co-chalcone methacrylate copolymer emulsion to obtain the methyl methacrylate-co-chalcone methacrylate copolymer.
Blending and extruding polymethyl methacrylate and polycarbonate to prepare a master batch, freezing and crushing the master batch in liquid nitrogen to obtain master batch powder with the average particle size of not more than 50 mu m, blending the master batch powder with a birefringence index regulator, an antioxidant and a dispersing agent, and feeding the mixture into a double-screw extruder through a feeding hopper to perform melt blending and extrusion to obtain a blend; wherein the temperature of the double-screw extruder is 225 ℃, and the extrusion rotating speed is 15 r/min; drying in a forced air oven at 110 deg.C; extruding the prepared blend on a single-screw extruder to form a film, wherein the temperature of the single-screw extruder is 225 ℃, and the extrusion speed is 60 r/min; and (3) rolling the cold roll at the temperature of 30 ℃, and discharging the sheet on the cold roll to obtain the optical film material.
Comparative examples 1,
Comparative example 1 is a commercially available PMMA (polymethylmethacrylate) material.
The following performance tests were performed on the materials of examples 1-6 and comparative example 1 as described above, using the following test methods: the density is tested according to the test standard of ISO 1183; the water absorption is tested according to the test standard of ISO 62; the surface hardness is tested according to the test standard GB/T6739-86; flexural modulus was tested according to ISO 178 test standard; the tensile strength is tested according to the test standard of ISO 527; the glass transition temperature is tested according to a DSC test method, and the specific test method comprises the following steps: under the protection of N2, heating a sample to be tested from normal temperature to 230 ℃ at a speed of 10 ℃/min, keeping the temperature at 230 ℃ for 3min to eliminate thermal history, then cooling to 30 ℃ at a speed of 10 ℃/min, standing at 30 ℃ for 3min, and then heating to 230 ℃ at a heating speed of 10 ℃/min; the refractive index is tested according to the test standard of ISO 489; the light transmittance was measured according to the test method of ISO 13468.
The birefringence refers to the difference between the refractive indexes of the two beams; specifically, the birefringence of the transparent material is a difference between the refractive indices of the TE mode (Transverse Electric mode) and the TM mode (Transverse Magnetic mode), and can be calculated by formula 1-1:
Δn＝nTE-nTM(1-1); wherein n isTEAnd nTMThe refractive indices of the medium in TE mode and TM mode, respectively.
The test results are detailed in table 1 below.
TABLE 1
As can be seen from table 1 above, compared with the conventional PMMA material sold in the market of comparative example 1, the optical film material prepared by the method of the present invention has significantly improved mechanical properties and high temperature resistance, and realizes positive and negative conversion of birefringence of different films, so that the material has a phase difference compensation function, and can meet the diversified demands of the market on optical films.
In addition, a large number of experiments show that the mechanical property, the high temperature resistance and the birefringence of the optical film material are obviously influenced by the types of polymethyl methacrylate and polycarbonate, the size of the crushed particle size after blending, the preparation method and the dosage of the birefringence regulator and the like, and the optical film material is specifically shown in the following comparative examples 2-5.
Comparative example 2
The raw materials and the preparation process conditions were the same as those in example 1 except that the copolymerized polymethylmethacrylate and the polycarbonate in example 1 were replaced with the non-copolymerized polymethylmethacrylate and polycarbonate in the same amount.
Comparative example 3
The raw materials and the preparation process conditions were the same as those in example 1 except that the master batch prepared by blending and extruding polymethyl methacrylate and polycarbonate was frozen and pulverized in liquid nitrogen to obtain a master batch powder having an average particle size of 60 μm.
Comparative example 4
The raw materials and the preparation process conditions were the same as in example 1, except that the method for synthesizing the birefringence modifiers was not emulsion polymerization.
The method for synthesizing the birefringence index adjuster used in comparative example 4 is as follows:
sequentially adding MMA, MSPK, initiator (azobisisobutyronitrile, AIBN) and reaction solvent N, N-Dimethylformamide (DMF) into a four-mouth bottle with a magnetic stirring rotor, introducing nitrogen for protection, setting the rotating speed of a magnetic stirrer to be 100rpm, heating to 90 ℃ under the protection of nitrogen for reaction for 2 hours, heating to 110 ℃, reacting for about 4 hours, cooling to room temperature when the solution has high viscosity, precipitating in methanol, performing suction filtration to obtain a milky polymer, performing vacuum drying at 60 ℃ for 24 hours, dissolving in chloroform, re-precipitating in methanol, performing suction filtration, and drying in a vacuum oven at 60 ℃ for later use to obtain the methyl methacrylate-co-chalcone methacrylate copolymer (birefringence index regulator).
Comparative example 5
The raw materials and the preparation process conditions were the same as in example 1, except that the amount of the birefringence modifier was adjusted to 0 part.
The optical film materials obtained in comparative examples 1 to 5 were subjected to performance tests with reference to the above test methods, and the test results are shown in Table 2 below.
TABLE 2
| Test items | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Density (g/cm)3) | 1.19 | 1.19 | 1.19 | 1.19 |
| Water absorption (%) | 0.24 | 0.25 | 0.25 | 0.25 |
| Surface hardness (Pencil) | 2H | 2H | 2H | 2H |
| Flexural modulus (MPa) | 2800 | 3225 | 3210 | 3100 |
| Tensile Strength (MPa) | 68 | 82 | 81 | 75 |
| Glass transition temperature (. degree. C.) | 118 | 126 | 123 | 115/202 |
| Refractive index | 1.52 | 1.52 | 1.52 | - |
| Light transmittance (%) | 87％ | 89％ | 88％ | 72％ |
| Double refractive index | 0.0001 | 0.0001 | 0.0001 | - |
As can be seen from the test results of tables 1 and 2 above, the effect of polymethyl methacrylate and polycarbonate on the flexural modulus, tensile strength, glass transition temperature and light transmittance of the material is large as seen from the comparison result of the performance of the optical film materials prepared in comparative example 2 and example 1, and the use of the copolymerized polymethyl methacrylate and polycarbonate is beneficial to improving the flexural modulus, tensile strength, glass transition temperature and light transmittance of the material.
The comparison result between the comparative example 3 and the example 1 and the preparation method thereof show that the optical film materials prepared in the examples 1 and 3 have small differences in mechanical properties, high temperature resistance and birefringence, but the light transmittance is enhanced, because the liquid nitrogen pulverization method is favorable for well controlling the particle size of the master batch and improving the blending effect of each phase, the transparency of the film is enhanced, and the particle size of the master batch is controlled within 50 μm, so that the transparency of the film is the best.
In addition, the emulsion polymerization method adopted in example 1 is used for synthesizing the birefringence regulator of the invention, the viscosity of the emulsion polymerization system is still very low after the reaction reaches a high conversion rate, the dispersion system is stable, compared with the method for synthesizing the birefringence regulator by adopting a non-emulsion polymerization method in comparative example 4, the proportion of MMA and MSPK in the system is easier to control, the conversion design of the positive and negative refractive indexes of the birefringence regulator is facilitated, the process is simpler, and the operation is easier. Meanwhile, in terms of performance, the optical film material prepared in example 1 has better light transmittance.
From the comparison result between comparative example 5 and example 1, it can be seen that the addition of the birefringence modifier prepared by the present invention is beneficial to improving the flexural modulus, tensile strength, glass transition temperature and light transmittance of the material, and can realize positive and negative birefringence transition of the film material, so that the material has a phase difference compensation function.
In addition, a large number of experiments show that the positive and negative random conversion of the birefringence of different films can be realized by adjusting the compounding ratio of MMA and MSPK in the birefringence regulator.
Specifically, on the basis of the above example 1, only the compounding ratio of MMA and MSPK in the birefringence modifier is changed by a single-factor test method, other raw materials and preparation process conditions of the birefringence modifier are fixed, so as to prepare each group of birefringence modifiers, and each group of optical film materials are prepared by using each group of birefringence modifiers according to the formula and preparation method of the above example 1, and then the birefringence of each group of optical film materials is tested by referring to the above test method. The test results are shown in table 3 below.
TABLE 3
In summary, in the preparation method of the optical film material provided by the embodiment of the invention, polymethyl methacrylate (PMMA) is used as a base material, Polycarbonate (PC) with high temperature resistance and high toughness and chalcone functional group polymethyl methacrylate resin (birefringence index regulator) which can be well dispersed in a material system and well compatible with materials in the system are introduced, and a twin-screw extruder and a single-screw extrusion film device are adopted for matching use, so that the PC and PMMA can be well compatible, the optical film material prepared by blending not only has good high temperature resistance, but also has a phase difference regulation function, the problem of single negative birefringence index of the conventional PMMA can be well solved, and the diversified requirements of the market on the optical film can be met. Meanwhile, the preparation method can realize continuous production, greatly improves the working efficiency, does not use a large amount of organic solvent in the whole preparation process, is green and environment-friendly, has wide market prospect, and is suitable for popularization and application.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for preparing an optical film material, comprising:
weighing the following components in parts by weight: 50-70 parts of polymethyl methacrylate, 15-35 parts of polycarbonate, 5-15 parts of birefringence regulator, 0.05-1 part of antioxidant and 0.5-2 parts of dispersant; wherein the birefringence regulator is chalcone functional group polymethyl methacrylate resin;
blending the polymethyl methacrylate, the polycarbonate, the birefringence regulator, the antioxidant and the dispersing agent, and then conveying the blended materials to a double-screw extruder for melt blending extrusion to obtain a blended material, wherein the temperature of the double-screw extruder is 225-290 ℃, and the rotating speed of the double-screw extruder is 15-100 r/min;
drying the blend, conveying the blend to a single-screw extruder, and extruding the blend to form a film to obtain an optical film material, wherein the temperature of the single-screw extruder is 225-285 ℃, and the extrusion speed is 10-100 r/min; the temperature of the winding cold roll is 30-80 ℃.
2. The method for preparing an optical film material according to claim 1, wherein the step of blending the polymethyl methacrylate, the polycarbonate, the birefringence modifier, the antioxidant and the dispersant and then conveying the blended mixture to a twin-screw extruder for melt blending extrusion comprises the following steps:
polymethyl methacrylate and polycarbonate are blended and extruded to prepare a master batch, the master batch is frozen and crushed in liquid nitrogen to obtain master batch powder with the average grain diameter of not more than 50 mu m, and the master batch powder is blended with a birefringence index regulator, an antioxidant and a dispersing agent and then conveyed to a double-screw extruder for melt blending and extrusion.
3. The method of claim 1, wherein the birefringence modifier is methyl methacrylate-co-chalcone methacrylate copolymer, and the method comprises the following steps:
under the protection of nitrogen, adding a mixture of methyl methacrylate and chalcone methacrylate into an emulsifier aqueous solution with the mass fraction of 0.1-0.5%, stirring and mixing uniformly, heating to 50-80 ℃, adding an initiator, and continuing to react until the reaction is finished to obtain methyl methacrylate-co-chalcone methacrylate copolymer emulsion;
and (3) freeze-drying the methyl methacrylate-co-chalcone methacrylate copolymer emulsion to obtain the methyl methacrylate-co-chalcone methacrylate copolymer.
4. The method for producing an optical film material according to claim 3, wherein the mixing mass ratio of methyl methacrylate and chalcone methacrylate in the mixture of methyl methacrylate and chalcone methacrylate is 1-4: 1-4.
5. The method of claim 1, wherein the average molecular weight of the birefringence modifier is 6-12 ten thousand, and the average particle size is not more than 50 μm.
6. The method of claim 1, wherein the polymethyl methacrylate is a copolymer polymethyl methacrylate, and the average molecular weight of the copolymer is 7 to 13 ten thousand.
7. The method for producing an optical film material according to claim 1, wherein the polycarbonate is a copolymer polycarbonate having an average molecular weight of 4.5 to 9 ten thousand.
8. The method of claim 1, wherein the antioxidant is a hindered antioxidant or a phosphite antioxidant;
the dispersant is at least one of siloxane dispersant, stearate dispersant or wax dispersant.
9. An optical film material, characterized in that the optical film material is prepared by the method for preparing the optical film material according to any one of claims 1 to 8.
10. A polarizer prepared by compounding the optical film material according to claim 9, a polyvinyl alcohol material and other functional films.
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